KR20210036961A - Polyethylene film - Google Patents

Abstract

A novel film is disclosed comprising a porous polyethylene membrane in which a hydrophilic polymer is absorbed to form a film having excellent durability. Films are useful for making articles, particularly textile laminates capable of forming waterproof breathable apparel.

Description

Polyethylene film

The present disclosure relates to waterproof, breathable polyethylene film composites useful in a variety of applications. The film may be used as such or may be laminated to another layer to form a multilayer laminate.

Clothing and other types of apparel, such as shoes, gloves and hats, often include a waterproof breathable layer to keep the wearer dry in humid conditions. These garments may be formed using a breathable waterproof layer and a laminate of one or more other textiles. Waterproof breathable films made using porous PTFE membranes and hydrophilic polyurethane are currently being used to manufacture GORE-TEX® textile laminates. PTFE membranes are microporous and generally hydrophobic, where the pore size of the membrane is larger than water molecules, but the pores are much smaller than individual water drops. Water vapor can pass through the material while water is prevented from passing from one side of the membrane to the other.

Although ePTFE membranes function well, porous polyurethane membranes have also been developed for use in apparel, but these membranes may lack durability and, in some cases, in certain commonly used products, such as nail polish or pesticides. Can be dissolved by These membranes may have restrictions that make the membrane stiff and noisy when the wearer moves. In addition to being excellent in waterproof and breathable properties, there is a continuous demand for the manufacture of a membrane having low noise and good tactile feel when an article including a membrane such as a garment is moved or bent.

In a first embodiment, the present disclosure provides that A) a) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene; b) a porosity of at least 40%; c) a porous polyethylene membrane comprising a Gurley number of less than 200 seconds; And B) a hydrophilic polymer filling at least a portion of the pores of the porous polyethylene, comprising: i) an MVTR of 2500 g/m 2 /day or more; ii) a weight of less than 30 grams/m2; In some cases, iii) it relates to a film comprising a Gurley number of 1000 seconds or more.

In a second embodiment, the present disclosure relates to the film of Embodiment 1 wherein the ratio of the matrix tensile strength of the film in two orthogonal directions is in the range of 0.5 to 2.0.

In a third embodiment, the present disclosure relates to the film of Embodiments 1 or 2, wherein substantially all of the pores of the porous polyethylene membrane are filled with a hydrophilic polymer.

In a fourth embodiment, the present disclosure relates to the film of any one of embodiments 1 to 3, wherein the hydrophilic polymer is a polyurethane, polyamide, polyester, ionomer, or copolymer or a copolymer or combination thereof.

In a fifth embodiment, the disclosure relates to the film of any one of embodiments 1 to 4, wherein the porous polyethylene membrane comprises a weight of less than 10 grams/m 2.

In a sixth embodiment, the disclosure relates to the film of any one of embodiments 1-5, wherein the porous polyethylene membrane comprises a porosity of at least 60%.

In a seventh embodiment, the present disclosure relates to the film of any one of embodiments 1-6, wherein the porous polyethylene membrane comprises a Gurley number of 60 seconds or less.

In an eighth embodiment, the present disclosure relates to the film of any one of embodiments 1 to 7, wherein the ratio of the matrix tensile strength of the film in two orthogonal directions ranges from 0.7 to 1.4.

In a ninth embodiment, the present disclosure provides that the polyethylene membrane has a first side and a second side, and a hydrophilic polymer is applied to the first side of the polyethylene membrane to fill at least a portion of the voids and a hydrophilic polymer on the first side of the polyethylene membrane. It relates to the film of any one of embodiments 1 to 8 which results in a cap of.

In a tenth embodiment, the present disclosure relates to the film of any one of embodiments 1 to 9, wherein the weight ratio of porous polyethylene to hydrophilic polymer is in the range of 30 to 0.5.

The present disclosure also relates to an article comprising the film of any one of embodiments 1-10.

In a twelfth embodiment, the disclosure relates to the article of Embodiment 11, wherein the article is a multilayer laminate comprising at least one other layer laminated to a film.

In a thirteenth embodiment, the disclosure relates to the article of embodiments 11 or 12, wherein at least one other layer is a textile layer, a polymer film layer, a natural leather layer, a synthetic leather layer, a fleece layer, or a combination thereof. will be.

In a fourteenth embodiment, the disclosure relates to the article of any one of embodiments 11 to 13, wherein at least one other layer is a textile layer.

In a fifteenth embodiment, the disclosure relates to the article of any one of embodiments 11-14, wherein the layers of the laminate are adhered to each other using a continuous or discontinuous adhesive.

In a sixteenth embodiment, the disclosure relates to the article of any one of embodiments 11-15, wherein the adhesive is a thermoplastic or crosslinkable adhesive.

In a seventeenth embodiment, the disclosure relates to the article of any one of embodiments 11 to 16, wherein the article is a garment.

In an eighteenth embodiment, the disclosure relates to the article of embodiment 17, wherein the garment is a jacket, coat, shirt, pants, gloves, hat, shoes, coveralls, or at least a portion thereof.

In a nineteenth embodiment, the disclosure relates to the article of embodiments 17 or 18, wherein the film is on the outside of the garment or the film is not on the outside of the garment.

In a twentieth embodiment, the disclosure relates to the article of any one of embodiments 17-19, wherein the garment is waterproof.

The present disclosure also relates to an article comprising a film.

The disclosures of all cited patent and non-patent documents are incorporated herein by reference in their entirety.

As used herein, the terms “embodiment” or “disclosure” are not intended to be limiting and apply generally to any embodiment defined in the claims or described herein. These terms are used interchangeably herein.

Unless otherwise disclosed, terms in the singular form used herein are intended to encompass one or more (ie, at least one) of the recited features.

Features and advantages of the present disclosure will be more readily understood by one of ordinary skill in the art upon reading the detailed description that follows. For the sake of clarity, it should be understood that certain features of the present disclosure described above and below in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, various features of the present disclosure that are described in combination in the context of a single embodiment may also be provided individually or in any subcombination. Furthermore, reference to the singular may also include the plural unless the context specifically dictates otherwise (eg, “a” and “an” may refer to one or more).

Unless otherwise specified, use of the numerical ranges of the various ranges specified in this application is described as an approximation, as if both the minimum and maximum values within the specified range were preceded by the word "about". In this way, a slight difference above and below the specified range can be used to achieve substantially the same results as the values within the range. Further, the disclosure of this range is intended as a continuous range including each and every value between the minimum and maximum values.

As used herein, the term "membrane" essentially means a polymer in the form of a two-dimensional sheet, where both the length and width are much greater than the thickness, for example both length and width are at least 100 times the thickness. In some embodiments, the membrane is a microporous membrane having a structure that allows water vapor to pass through the thickness of the membrane while, for example, preventing liquid water from penetrating from one side of the membrane to the other. On average, the pore size ranges from a few nanometers to about 1 micrometer.

The term “film” refers to a membrane in which the pores are at least partially filled with a polymer such that no flow of gas or liquid occurs through the open pore channels of the membrane. In some embodiments, the polymer that at least partially fills the voids may be a hydrophilic polymer.

The term "hydrophilic polymer" refers to a polymer that is capable of allowing a significant amount of water to pass through the film by absorbing water on one side of the film with a high moisture concentration and desorbing or evaporating it on the opposite side of the film with a low water vapor concentration. Refers to. In some embodiments, a layer of hydrophilic polymer that is 10 microns thick may have a water vapor transmission rate of at least 5,000 g/m 2 /day, or at least 10,000 g/m 2 /day.

The phrases “porous polyethylene membrane” and “polyethylene membrane” are used interchangeably throughout the specification. Unless specifically stated otherwise, both phrases are: a) at least 30% by weight of the porous polyethylene has a weight average molecular weight ^{greater than 0.5x10 6 g/mol;} b) a porosity of at least 40%; c) It means a porous polyethylene membrane having a Gurley number of less than 200 seconds or less than 100 seconds. When enlarged, the porous polyethylene membrane shows the fibrillated structure of polyethylene fibrils, and one or more polyethylene fibrils can be seen at a sufficient magnification, and in some cases, three or more fibrils are at least one intersection of three or more fibrils. Can be interconnected by

As used herein, the term “polyethylene” refers to a polyethylene polymer having less than 5% by weight of one or more comonomers. In some embodiments, the polyethylene does not contain a fluorine-containing comonomer, and in further embodiments, the polyethylene is a polyethylene homopolymer.

The present disclosure relates to a film comprising A) a porous polyethylene membrane and B) a hydrophilic polymer filling at least a portion of the voids of the porous polyethylene membrane. This film does not leak due to contamination by oils, detergents or other contact angle reducing substances, and is self-waterproof. Moreover, articles comprising films have greater durability in the field and in laundry than other non-breathable hydrophilic films that do not include porous polyethylene membranes as structural supports. Porous polyethylene is a membrane in which at least 30% by weight of polyethylene has ^{a weight average molecular weight of greater than 0.5x10 6} grams/mole (g/mol). In some embodiments, the porous polyethylene comprises at least 30% by weight polyethylene having a weight average molecular weight greater than ^{0.75x10 6 g/mol.} In a further embodiment, the porous polyethylene comprises at least 30% by weight of polyethylene having a weight average molecular weight greater than 1.0x10 ^{6 g/mol.} In a further embodiment, at least 40% by weight of polyethylene 0.5x10 ⁶ g / mole (g / mol) has the weight-average molecular weight of greater than, or at least 50% by weight of polyethylene exceeds 0.5x10 ⁶ g / mole (g / mol) It has a weight average molecular weight of. All weight percentages are based on the total weight of the porous polyethylene membrane. In some embodiments, the porous polyethylene has a weight average molecular weight greater than 750,000 g/mol. In a further embodiment, the porous polyethylene has a weight average molecular weight greater than 1,000,000 g/mol. In a further embodiment, the polyethylene has a weight average molecular weight of greater than 1,500,000 grams/mole or greater than 1,750,000 grams/mole. In further embodiments, the polyethylene has a weight average molecular weight greater than 2,000,000 grams/mole, 3,000,000 grams/mole, 4,000,000 grams/mole, 5,000,000 grams/mole, or 8,000,000 grams/mole.

The polyethylene membrane is a porous polyethylene membrane having a porosity of at least 40%. In some embodiments, the porosity of the porous polyethylene membrane can be at least 50% or at least 60% or at least 70% or at least 80%. The porosity of the membrane, φ is the mass per unit area of the membrane, MPA, and the thickness of the membrane, t are measured, and the relationship of φ = (1- MPA/(t*ρ))*100 (where ρ is the density of the membrane polymer) is used. Can be calculated by The porous polyethylene membrane may also have a Gurley value of less than 200 seconds or less than 100 seconds or less than 90 seconds or less than 80 seconds or less than 70 seconds or less than 60 seconds or less than 50 seconds or less than 40 seconds or less than 10 seconds.

The porous polyethylene membrane may have a relatively light weight of, for example, 10 grams/m 2 (gsm) or less. In other embodiments, the porous polyethylene membrane may have a weight of 9 gsm or less or 8 gsm or less or 7 gsm or less or 6 gsm or less or 5 gsm or less or 4 gsm or less or 3 gsm or less or 2 gsm or less.

The porous polyethylene membrane may or may not be colored. The use of a porous polyethylene membrane can provide an aesthetic quality of great value to the film and the article comprising the film, especially when the porous polyethylene membrane is visible on the article. Any of the known coloring methods can be used. For example, the porous polyethylene membrane can be colored over most of the membrane through the addition of a pigment or dye during the film formation process. In other embodiments, the porous polyethylene membrane may be colored after formation through known printing and dyeing processes. In further embodiments, the porous polyethylene membrane may be free or essentially free of any added color, and color may be added in one or more steps during the film forming process described herein.

The film also includes B) a hydrophilic polymer that fills at least a portion of the voids of the porous polyethylene membrane. The phrase “filling at least a portion of the void” means filling the void until the point where the hydrophilic polymer is absorbed into the void of the polyethylene membrane and no airflow can be determined through the region of the film containing the hydrophilic polymer (which may take 1000 seconds or more). . That is, the hydrophilic polymer is not a mere coating on the wall of a polyethylene film defining the pores. Although some voids may be present, it is believed that the hydrophilic polymer forms a continuous layer within the region of the porous polyethylene membrane to which the hydrophilic polymer is applied. In other embodiments, the hydrophilic polymer forms a continuous layer free of or essentially free of any voids within the region of the porous polyethylene membrane to which the hydrophilic polymer is applied. In a further embodiment, substantially all of the pores of the porous polyethylene membrane are filled with a hydrophilic polymer.

The polyethylene membrane has a first side and a second side. The hydrophilic polymer can be applied to the first side of the porous polyethylene membrane, and the hydrophilic polymer can penetrate at least a portion of the voids to form a film, and as a result, can fill at least a portion of the voids of the polyethylene membrane. The first side of the polyethylene membrane may include a cap layer of a hydrophilic polymer on the outside of the membrane. The cap layer or amount of the hydrophilic polymer on the first side of the porous polyethylene membrane has essentially no upper limit. However, if the cap layer is too thick, the advantageous properties of the porous polyethylene membrane cannot be realized, and thus the upper limit of the cap is about 50 micrometers. In some embodiments, the cap layer of the hydrophilic copolymer may be up to 40 micrometers or up to 30 micrometers or up to 20 micrometers or up to 15 micrometers thick at the first surface of the polyethylene membrane. In some embodiments, the cap layer of the hydrophilic polymer can be up to about 10 microns thick at the first surface of the polyethylene membrane. In other embodiments, the cap layer on the first side of the polyethylene membrane has a thickness of 10 micrometers or less, or 8 micrometers or less or 6 micrometers or less, or 4 micrometers or less or 2 micrometers or less. In a further embodiment, there is no cap layer of the hydrophilic copolymer on the first surface of the polyethylene membrane. The second side of the polyethylene membrane may be essentially free of hydrophilic polymers on its surface, for example no hydrophilic polymers of a thickness exceeding 1 micrometer on the surface of the polyethylene membrane. In some embodiments, less than the total thickness of the porous polyethylene membrane is filled with a hydrophilic polymer, e.g., up to 90% of the thickness of the polyethylene membrane may be filled with a hydrophilic polymer, provided that the porous polyethylene film has a duration of 1000 seconds or more. Sufficient hydrophilic polymer is absorbed to provide. In other embodiments, essentially the entire thickness of the porous polyethylene membrane is filled with a hydrophilic polymer. As used herein, the phrase “essentially full thickness” means that at least 90% of the thickness of the porous polyethylene membrane is filled with a hydrophilic polymer. In other embodiments, the hydrophilic polymer can be applied to the second side as well as the first side of the polyethylene membrane. The hydrophilic polymer applied to the second side may be the same as or different from the hydrophilic polymer applied to the first side. In a further embodiment, the film has a hydrophilic polymer applied to the first side of the first porous polyethylene membrane having a sufficient amount of hydrophilic polymer to form the cap layer by being applied to the first side of the porous polyethylene membrane, and thereafter, the first porous polyethylene The second porous polyethylene membrane, which may be the same as or different from the membrane, may be a composite film bonded to the laminate through a cap layer of a hydrophilic polymer. This can result in a three-layer structure with two porous polyethylene films bonded to each other by a hydrophilic polymer as a layer between two porous polyethylene films. If desired, additional layers or layers of hydrophilic polymer may be applied to one or both of the outside of the composite film.

In some embodiments, the hydrophilic polymer may be applied to the porous polyethylene membrane in a continuous manner such that essentially 100% of the surface area of the porous polyethylene membrane comprises the hydrophilic polymer. As used herein, the term “continuous” means that the entire width or nearly the entire width of the porous polyethylene membrane is coated with a hydrophilic polymer. It should be noted that in many coating processes, the edges of the roll of material are not coated due to the frame or dam at the edges, so that the entire width of the film is not coated. In other embodiments, the hydrophilic polymer can be applied to the porous polyethylene membrane in a discontinuous manner. As used herein, the term “discontinuous” means that less than 100% of the surface area of the porous polyethylene membrane is coated with a hydrophilic polymer and some of the non-edge regions of the porous polyethylene membrane contain no hydrophilic polymer. For example, a hydrophilic polymer applied to a porous polyethylene membrane as a series of dots or as a lattice of orthogonal lines is considered a discontinuous coating. The area% of the porous polyethylene membrane filled with the hydrophilic polymer is 20% or more 100% or 30% to less than 100% or 40% to less than 100% or 50% to less than 100% or 60 to less than 100% or 70 to less than 100% or It may range from 80 to less than 100% or from 90 to less than 100%. In other embodiments, the application of the hydrophilic polymer is carried out in a manner that creates a random or non-random pattern of dots, polygons, parallel lines, intersecting lines, straight lines, curves, or any combination thereof to provide a range of desired area percent. I can. Where oleophobicity is desired in such films, in certain embodiments, it may be desirable to include an oleophobic coating, as otherwise described herein.

As a weight ratio, the film may have a ratio of the weight of the hydrophilic polymer to the weight of the porous polyethylene membrane in the range of 30.0 to 0.5. In another embodiment, the weight ratio of the hydrophilic polymer to the polyethylene membrane is 20.0, 15.0, 10.0, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5 or above It can be any weight ratio between.

Suitable hydrophilic polymers may include, for example, polyurethanes, polyamides, polyesters, ionomers, or copolymers or combinations thereof. In other embodiments, almost any suitable hydrophilic polymer can be used as long as the hydrophilic polymer can have a water vapor transmission rate of at least 5,000 grams/m 2 /day or at least 10,000 grams/m 2 /day. The hydrophilic polymer can be a thermoplastic or crosslinkable polymer. In some embodiments, the hydrophilic polymer is a polyurethane, and in further embodiments, the polyurethane is a crosslinked polyurethane. Suitable polyurethane polymers can be, for example, polyesterurethane, polyetherurethane or polyether-polyesterurethane.

In some embodiments where coloration is desired, color can be added, for example, using a colored hydrophilic polymer in which a pigment or dye is added to the hydrophilic polymer, resulting in a film having the desired color. In other embodiments, the porous polyethylene film may be colored during formation of the porous polyethylene film according to known methods, for example, master-batch treatment. Thus, one or both of the porous polyethylene membrane and the hydrophilic membrane may or may not be colored. When both the porous polyethylene and the hydrophilic polymer are colored, they can be colored in the same or similar shades or can be selected in color independently of each other. Any known pigment or dye may be used including organic pigments and dyes, inorganic pigments or dyes, metals, metal oxides, carbon black, titanium dioxide or combinations thereof.

In a further embodiment, the porous polyethylene membrane can be treated with both oleophobic and hydrophilic polymers. For example, in a first step, the first side of the porous polyethylene membrane may be treated with an oleophobic polymer capable of coating the walls defining the pores of the porous polyethylene membrane without filling the pores, wherein less than the total thickness of the porous polyethylene membrane. An oleophobic polymer is provided to be treated with this oleophobic polymer. After the optional drying and curing step for the oleophobic polymer, the second side of the porous polyethylene membrane is treated with a hydrophilic polymer to fill at least a portion of the remaining thickness of the porous polyethylene membrane, and then selective heating and The curing step can be performed. In these embodiments, the hydrophilic polymer fills only the portion of the porous polyethylene membrane that does not have an oleophobic treatment because the hydrophilic polymer does not wet the oleophobic treated portion of the porous polyethylene membrane.

In some embodiments, the porous polyethylene membrane may be treated with an oleophobic polymer through at least 5% of the thickness of the porous polyethylene membrane. In other embodiments, the porous polyethylene membrane may include an oleophobic treatment through up to 95% of its thickness. In a further embodiment, the oleophobic treatment may be present in the range of 10 to 90% of the thickness of the porous polyethylene membrane or 10 to 80%, or 10 to 70% or 10 to 60% or 10 to 50% of the thickness of the porous polyethylene membrane. Or 10 to 40% or 10 to 30% or 10 to 20%. After treatment of the first side of the porous polyethylene membrane, the second side of the porous polyethylene membrane may be treated with a hydrophilic polymer, which may fill any remaining thickness of the porous polyethylene membrane, and in some embodiments, form a cap layer of the hydrophilic polymer. .

The final film comprising a porous polyethylene membrane and a hydrophilic polymer has a water vapor transmission rate (MVTR) of 2500 grams/m2/day (g/m2/day) or more; It can have a weight of less than 30 grams/m2 and, in some cases, a Gurley number of 1000 seconds or more. In order to have breathability, that is, to allow water vapor to move from one side of the film to the other without moving liquid water through the film, the MVTR may be 2500 g/m 2 /day or more. In other embodiments, the film has an MVTR of at least 3000 g/m 2 /day, at least 3500 g/m 2 /day, at least 4000 g/m 2 /day, at least 4500 g/m 2 /day, at least 5000 g/m 2 /day, 5500 g/m²/day or more, 6000 g/m²/day or more, 6500 g/m²/day or more, 7000 g/m²/day or more, 7500 g/m²/day or more, 8000 g/m²/day or more, 8500 g/ It may be at least 9000 g/m 2 /day, at least 9500 g/m 2 /day, or at least 10,000 g/m 2 /day.

The film may also have a ratio of matrix tensile strength in two orthogonal directions ranging from 0.5 to 2.0. In other embodiments, the ratio of the matrix tensile strength in two orthogonal directions may range from 0.7 to 1.4. In further embodiments, the ratio of tensile strength is 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 or any value between the two values. I can. The difference in tensile strength in the two orthogonal directions is related to the difference in the total strain applied in the two directions during the film manufacturing process.

The film may also be stain resistant due to the presence of a hydrophilic polymer filling the voids in at least a portion of the film thickness, thereby forming a void-free continuous layer in that portion of the porous polyethylene membrane. Staining resistance as used herein means that the film is not contaminated with sweat, sebum or oil, so that the waterproofing property does not deteriorate over time. If at least some of the pores of the porous polyethylene membrane are left unfilled, the oleophobic coating on the walls of the unfilled pores can provide fouling resistance to the unfilled pores.

This disclosure also

1) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight of greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene, a porosity of at least 40%, and can take less than 200 seconds. Providing a porous polyethylene membrane having a;

2) Coating at least a portion of the porous polyethylene membrane with a hydrophilic polymer; And

3) Optionally, crosslinking the hydrophilic polymer

It relates to a method for producing a film comprising a porous polyethylene membrane and a hydrophilic polymer comprising a.

In another embodiment, the film can be made according to the following steps:

1) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight of greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene, a porosity of at least 40%, and can take less than 200 seconds. Providing a porous polyethylene membrane having a;

2) Coating a wall defining the pores of the porous polyethylene membrane by coating the first side of the porous polyethylene membrane with an oleophobic polymer;

3) Forming a film by coating a second surface of the porous polyethylene film with a hydrophilic polymer; And

4) Optionally, crosslinking the hydrophilic polymer.

The film may also be stain resistant due to the presence of a hydrophilic polymer filling the voids in at least a portion of the film thickness, thereby forming a void-free continuous layer in that portion of the porous polyethylene membrane. Staining resistance as used herein means that the film is not contaminated with sweat, sebum or oil, so that the waterproofing property does not deteriorate over time. If at least some of the pores of the porous polyethylene membrane are left unfilled, the oleophobic coating on the walls of the unfilled pores can provide fouling resistance to the unfilled pores.

The present disclosure also relates to an article comprising the film. One advantage of the article of the present disclosure is that the article is durable to wash. As used herein, the term “laundry durability” refers to a laminate comprising the disclosed film can be washed according to the laundry durability testing procedure disclosed herein for at least 15 hours and the laminate is determined according to the Suter test described herein. It means that it is waterproof together. In other embodiments, the laminate maintains laundry durability after washing for at least 50 hours or at least 100 hours. In some embodiments, the laminate did not leak after at least 200 hours of washing testing. Articles can also be waterproof and breathable.

In some embodiments, an article can be made according to the following steps:

1) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight of greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene, a porosity of at least 40%, and can take less than 200 seconds. Providing a porous polyethylene membrane having a;

2) Coating at least a portion of the porous polyethylene membrane with a hydrophilic polymer;

3) Laminating the film to at least one other layer; And

4) Optionally, crosslinking the hydrophilic polymer.

In other embodiments, the article can be made according to the following steps:

1) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight of greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene, a porosity of at least 40%, and can take less than 200 seconds. Providing a porous polyethylene membrane having a;

2) Laminating at least one other layer to the first side of the porous polyethylene membrane;

3) Coating at least a portion of the second side of the porous polyethylene membrane with a hydrophilic polymer; And

4) Optionally, crosslinking the hydrophilic polymer.

The article may be a multilayer laminate, for example one or more layers of a film, and one or more other layers laminated together to form a laminate. The one or more other layers may be a textile layer, a polymer film layer, a natural leather layer, a synthetic leather layer, a fleece layer, or a combination thereof. One or more of the layers may be a textile layer, a film layer, or a combination thereof. In some embodiments, the article can be a two-layer laminate comprising a textile layer adhered to the first or second side of the film. In some embodiments, the article can be a three-layer laminate comprising a first textile layer bonded to a first side of the film and a second textile layer bonded to a second side of the film. In further embodiments, additional layers may be applied to create a multilayer laminate having 4, 5, 6 or more layers. Suitable textile layers can include any woven, knitted or nonwoven textile. The textile may be natural and/or synthetic, for example cotton, wool, silk, jute, polyamide, polyester, acrylic, aramid, viscose, rayon, carbon fiber or combinations thereof. Suitable polymeric films include, for example, polyolefins, polyesters, polyamides, polyurethanes, polyvinyl alcohols, polyvinyl acetates, fluoropolymers, polyvinyl halides, polyvinyl chlorides, epoxy resins, silicone polymers or combinations thereof. Can include. Laminates comprising one or more layers of the disclosed films, one or more textile layers and/or one or more polymer film layers may also be prepared.

Due to the high strength of the disclosed films, any textile or material listed above and having a relatively low mass can be used to make the laminate. In some embodiments, the laminate may comprise a relatively low mass textile having a basis weight in the range of 5 grams/m 2 to 30 grams/m 2 (gsm). In other embodiments, the textile is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 , 28, 29 or 30 gsm, or any value between two of these values. Although relatively low mass textiles can be used, textiles having a weight of 30 gsm or more can also be used. For example, relatively high mass textiles with masses as high as 500 gsm can be used.

Lamination techniques are well known in the art and may include, for example, adhesive lamination, thermal bonding and stitching. If a waterproof laminate is required, stitch bonding may be undesirable unless care is taken to make the stitch holes impermeable to liquid water, for example by sealing the stitch holes using seam tape. In some embodiments, lamination is achieved by adhesive lamination, wherein the adhesive is applied to one or more layers to be bonded together, and the layers are then applied to heat and/or pressure as the case may be, for example via a nip roller. By, are placed together. The adhesive may be applied to the film layer, the textile layer, or both the film layer and the textile layer. The adhesive may be applied in a discontinuous manner, for example in a series of adhesive dots, shapes, lines, or combinations thereof. In other embodiments, the adhesive can be applied as a continuous layer of adhesive. The adhesive composition may be a thermoplastic or crosslinkable adhesive in certain embodiments. In a further embodiment, the hydrophilic polymer can be used as an adhesive material for the formation of laminates. For example, after applying the hydrophilic polymer to one side of the porous polyethylene membrane while forming the cap layer of the hydrophilic polymer, the textile can be applied to the hydrophilic polymer, and heat and/or pressure is applied to the laminate so that the hydrophilic polymer is in sufficient contact with the textile. It can be guaranteed to be glued. If a hydrophilic polymer is used as an adhesive for lamination, a curing step for the hydrophilic polymer may be performed after a textile or other material is placed on the side of the film containing the hydrophilic polymer cap layer. In some embodiments, a hot press can be used to provide sufficient pressure to allow the hydrophilic polymer to flow into the space between the textile fibers, and the heat from the hot press can perform the desired curing and heat treatment steps to create the laminate. . In other embodiments, one or more rollers may provide the necessary pressure and/or heat to perform the same operation, for example in a continuous manner.

Laminates having stretch and recovery properties can be produced by known methods. For example, U.S. Patent No.4443511, U.S. Patent No.9950504, U.S. Patent No.9126390, U.S. Patent No.9233520, U.S. Patent No.9238344,WO 2018/67529 (the contents of which are incorporated herein by reference in their entirety Included), all teach methods of imparting stretch to existing membrane and laminate constructions, these teachings may be adapted to provide stretch to laminates comprising the film(s) of the present disclosure. .

Articles may be of, for example, garments, enclosures, protective enclosures, tents, sleeping bags, bebe bags, backpacks, packs, covers and other similar types that benefit from the properties of the films of the present disclosure. The garment may be a jacket, coat, shirt, pants, gloves, hat, shoes, coveralls, or at least a portion thereof. Many articles are made of a plurality of panels that are sewn or otherwise bonded together to form a finished product. Thus, “at least a portion” of an article means that at least one panel or a portion of the panel comprises the disclosed film. Articles and garments can be made such that the film is on the outside of the garment, on the inside of the garment, or so that the film is at least one of the middle layers of the garment, for example an middle layer of a three-layer laminate. One advantage of articles and garments comprising the disclosed films is their washability. Another advantage of the garment is that it can be waterproof and breathable.

For embodiments where the film is on the outside of the garment, meaning that the film is the outermost part of the garment, the film is colored, uncolored, the film is textured, the film is embossed, or any combination thereof. It can be used to create the desired appearance. Methods of coloring the films are described herein. In order to emboss the film, the film may optionally be compressed in a random or non-random manner, for example, a pattern, a letter, a word, a picture, a sports team logo, a business logo, or a combination thereof, a hydrophilic polymer May be embossed into the film or film prior to the treatment of or after treatment of the hydrophilic polymer or in both cases. Selective compression may result in other translucent areas of the film, which can also change the breathability of the film, and the embossed areas have a relatively lower breathability than the non-embossed areas. Suitable embossing methods can be found in US Publication No. 20080143012, the entire contents of which are incorporated herein by reference.

For embodiments where the film is on the outside of the garment, meaning that the film is the outermost portion of the garment, at least a portion of the film may be textured. The film can be textured by treating the film with a random or non-random pattern of abrasion resistant polymer. The abrasion resistant polymer can be applied in a series of dots, lines or other shapes to provide improved abrasion resistance to the outermost part of the garment as well as to provide a desired appearance. Suitable abrasion resistant polymers and methods of application thereof can be found in US Publication No. 2010/0071115, which is incorporated herein by reference in its entirety. Another method of texturing the film may include applying a flock to at least a portion of the film. Suitable methods for the application of flock materials can be found in WO 99/39038, the entire contents of which are incorporated herein by reference.

It has also been found that films and articles, such as laminates comprising films, can provide essentially permanent wrinkles without the need for additional chemicals currently in use. This may be particularly useful for garments comprising a film and at least one textile layer, for example trousers. The laminate comprising the film and textile placed on the embroidery hoop and cooled after heating was confirmed to show wrinkles in the portion of the laminate fixed to the embroidery hoop when the laminate was removed from the embroidery hoop. The heating temperature is 125°C or higher, or 130°C or higher and 180°C or lower. In embodiments where wrinkles are desired, for example in garments, wrinkles can be made by folding the article and pressing it with heat.

Example

Test Methods

Molecular Weight

Molecular weight determination was performed according to the procedure provided in Mead, D. W., Determination of Molecular Weight Distributions of Linear Flexible Polymers from Linear Viscoelastic Material Functions, Journal of Rheology 1994, 38(6): 1797-1827.

Porosity

The porosity was expressed as% porosity, and was determined by subtracting the quotient of the average density of the porous polyethylene membrane and the true density of the polymer from 1, and multiplying the value by 100. For this calculation, the true density of polyethylene was taken to be 0.94 grams per cubic centimeter. The density of the sample was calculated by dividing the mass/area of the sample by the thickness.

Water Vapor Permeability Test Protocol (MVTR)

The MVTR is measured according to DIN EN ISO 15496 (2004). This is a standard test used in the textile industry, reference is made to the detailed description of the MVTR test disclosed in DIN EN ISO 15496 (2004). For the description of the MVTR test, reference is also made to WO 90/04175 A1.

The basic principles are summarized as follows. The sample to be tested is inserted into an annular sample holder with a highly water vapor permeable but waterproof microporous membrane. Thereafter, the support is immersed in water for 15 minutes (deionized water at 23°C) so that the membrane is in contact with water. The cup is filled with a saturated solution of potassium acetate in water to create a relative humidity of 23% at the surface of the sample and covered with a second piece of the same waterproof microporous membrane. The cup containing the potassium acetate solution and the second membrane is weighed and then placed on the sample holder so that the second membrane is in contact with the sample. It transfers water vapor from the water side through the sample to the cup with potassium acetate. After 15 minutes, the cup with potassium acetate is removed and its weight is determined. To determine the water vapor transmission rate of the test setup without a sample, the first and second membranes are used, but the same procedure is performed without a sample. Then, taking into account the influence of the two additional microporous membranes, the MVTR of the sample can be determined from the difference between the two measurements.

The water vapor transmission rate (MVTR) of the laminate according to the present invention was measured according to EN ISO 15496 (2004) and is expressed in g/m2/24hr. In order to be considered water vapor permeable as used herein, the laminate should generally have a water vapor transmission rate of at least 3000 g/m 2 /24 hr, preferably at least 8000 g/m 2 /24 hr, more preferably at least 12000 g/m 2 /24 hr. do. The MVTR value can be as high as 20000 g/m2/24hr.

Girly

The Gurley airflow test measures the time it takes in seconds for 100 cm 3 of air to pass through a 6.45 cm 2 sample at a water pressure of 12.4 cm. Samples were measured on a Gurley Densometer Model 4110 automatic densometer equipped with a Gurley Model 4320 automated digital timer. Reported results are the average of multiple measurements.

Matrix Tensile Strength (MTS)

To determine the MTS, the sample membrane was cut in the longitudinal and transverse directions using ASTM D412-Dogbone Die Type F (DD412F). ^{Tensile breaking loads were measured using an INSTRON ®} 5500R (Illinois Tool Works Inc., Norwood, MA) tensile tester equipped with a flat grip and a "200 lb" (~90.72 kg) load cell. The gage length of the grip was set to 8.26 cm and a strain of 0.847 cm/s or 14.3 %/s was used. After placing the sample in the grip, the sample was retracted by 1.27 cm to obtain a baseline, and then a tensile test was performed at the aforementioned strain. For each condition, two samples were tested individually and the average of the maximum load (ie, maximum force) measurements was used in the MTS calculation. The longitudinal and transverse MTS were calculated using the following equation:

MTS = (maximum load / cross-sectional area) * (polymer true density / membrane density).

Laundry test

The Kenmore Series 80 washing machine has been changed so that a timer can be set to keep the machine running for a specified time. Washing durability was performed by washing the laminate samples in a modified Kenmore washing machine with no laundry detergent set to high load, cold water and high strength cycles for the desired time. When the sample has been washed for the desired time, it is removed from the washing machine and dried at ambient conditions.

Shooter test

The shooter test method was used to determine if the sample was liquid-resistant. This procedure is generally based on the description of ASTM D 751-00, Standard Test Method for Coated Fabrics (Hydrostatic Resistance Procedure B2).

The test sample was clamped and sealed between a rubber gasket of a fixture holding the sample so that water could be applied to a specific area. The circular area to which the water was applied was about 10.8 cm (4.25 inches) in diameter. Water was applied to one side of the sample at a pressure of 0.07 bar (1 psig). When testing a laminate with one textile layer, pressurized water was incident on the film side.

The unpressurized side of the sample was visually observed for traces of water appearing for 3 minutes. If no water was observed, the sample was considered to have passed the test and was considered liquid-proof. The reported value was the average of three measurements.

Example 1

Polyethylene consisting of polyethylene having a weight average molecular weight of 3,150,000 grams/mol (g/mol), more than 30% by weight of the porous polyethylene membrane having a weight average molecular weight of more than 500,000 g/mol, and having a porosity of 64.9% and a take time of 68.0 seconds The film was laminated to the polyester fabric so that the polyurethane adhesive covered approximately 35% of the film surface area using a non-permeable polyurethane adhesive applied in a discrete dot pattern using a gravure coating roll. The polyurethane adhesive was cured.

A film of this two-layer (2L) laminate was gravure coated with 17 gsm of a hydrophilic polyurethane prepolymer mixture containing a heat activated curing agent and passed through an infrared oven for approximately 20 seconds to activate the curing agent and crosslink the polyurethane. Then, the film was rolled up. The polyurethane coated 2L laminate was cooled to room temperature and cured.

Thereafter, a sample of the two-layer (2L) laminate was tested for durability during washing. In the first test, a 2L laminate sample was placed in a water-only home washing machine. The washing machine was turned on and kept running for 24 hours. Thereafter, the sample was taken out, hung on a rack, and dried for 24 hours. The samples were then tested for leaks in three separate 4 inch diameter circular areas by applying a hydraulic pressure of 1 psi to one side of the laminate for 3 minutes. No leaks were found in any of the three areas of the sample. The 2L laminate was returned to the washing machine and the test was repeated until a total washing time of 216 hours was completed. When 1 psi of water pressure was applied for 3 minutes, no leaks were seen in any of the three circular areas. In the second test, 2L laminate samples were washed in a household washing machine and then dried in a household dryer. This process was repeated for a total of 5 complete washing and drying cycles. The samples were then tested for leaks in three separate 4 inch diameter circular areas by applying a hydraulic pressure of 1 psi on one side for 3 minutes. No leaks were seen in any of the three circular areas. The sample was returned to the washer and the test was repeated for 10 washing and drying cycles. No leaks were seen in any of the three circular areas of the sample after applying a water pressure of 1 psi for 3 minutes.

Comparative Example A

A 30 micron thick polyethylene membrane (available from Gelon LIB Co., Ltd in China) with a weight average molecular weight of 769,000 g/mol of polyethylene is stretched in the machine direction (MD) 2.25:1 and then in the transverse direction (TD) 9:1 Stretched to. The resulting PE membrane had a mass per unit area of 2.1 grams/m 2 (gsm), a thickness of 10 microns, a Gurley time of 7.5 seconds, and a porosity of 78%. This stretched film was laminated to a polyester fabric (available from Nanya, article #J47P) using a water-impermeable polyurethane adhesive applied in a discrete dot pattern using a gravure coating roll. The polyurethane adhesive covered approximately 35% of the membrane surface area. This two-layer (2L) laminate was cured in roll form for 2 days.

Thereafter, the film of this 2L laminate was gravure coated with 17 gsm of a hydrophilic polyurethane prepolymer mixture containing a heat activated curing agent. The polyurethane coated laminate was passed through an infrared oven for approximately 20 seconds to activate the curing agent and crosslink the polyurethane to create a viscous surface. Then, the film was rolled up. The rolls of the polyurethane coated laminate were allowed to cure completely in roll form for 2 days.

A sample of this 2L laminate was tested for durability in washing. In the first test, a 2L laminate sample was placed in a water-only home washing machine. The washing machine was turned on and kept running for 24 hours. Thereafter, the sample was taken out, hung on a rack, and dried for 24 hours. The samples were then tested for leaks in three separate 4 inch diameter circular areas by applying a hydraulic pressure of 1 psi to one side of the laminate for 3 minutes. Leakage was found in 3 areas of the sample. In the second test, 2L laminate samples were washed and dried according to the procedure described above. This process was repeated for a total of 5 complete washing and drying cycles. The samples were then tested for leaks in three separate 4 inch diameter circular areas by applying a hydraulic pressure of 1 psi on one side for 3 minutes. Leakage was observed in two of the three circular regions.

Example 2

A polyethylene resin having a weight average molecular weight of about 7,000,000 grams/mole from Mitsui Chemicals, Inc., prepared according to WO 2012/053261, was made into a film according to the process described in U.S. Patent No. 9,926,416. The resulting membrane had a mass of 2.4 grams/m 2 and a porosity of 62.5%. A composite film was prepared by coating the membrane with 5.1 grams/m 2 of a hydrophilic polyurethane prepolymer mixture containing a heat activated curing agent, and then heating the film in an infrared oven set at a temperature of 130° C. to activate the curing agent and crosslinking the polyurethane. Thereafter, a two-layer (2L) laminate was formed by laminating the film to a polyester fabric using a non-permeable polyurethane adhesive. The impermeable polyurethane adhesive was applied in a discrete dot pattern using a gravure coating roll so that the polyurethane adhesive covered approximately 35% of the membrane surface area.

Thereafter, a sample of the two-layer (2L) laminate was tested according to the washing durability test. The washing machine was turned on and kept running for 68.5 hours. Thereafter, the sample was taken out, hung on a rack, and dried for 24 hours. The samples were then tested for leaks using the shooter test in five individual 4 inch diameter circular areas. No leaks were found in any of the five circular areas. The laminate was returned to the washing machine and the washing machine continued to run for 54.75 hours. The laminate was again leak tested and no leaks were observed in any of the five circular areas. The laminate was returned to the washing machine and the washing machine continued to run for 113.5 hours. The laminate was again leak tested and no leaks were observed in any of the five circular areas. The total time for the laundry test was 236.75 hours.

Comparative Example B

I bought a Columbia Omni-Dry Peak 2 Peak Waterproof Jacket (Columbia Sportswear Company). The garment was a 3L laminate, containing outer and inner textiles, both of which were laminated to a polyethylene membrane. The back of this jacket was cut off and the laminate was tested for durability by washing the machine continuously for 15.25 hours. Three separate 4 inch diameter circular areas of the laminate were tested according to the shooter test. There were no seams in these circular areas. Several leaks were found in all three circular areas.

Claims (20)

A) a) at least 30% by ^{weight of the porous polyethylene has a weight average molecular weight greater than 0.5x10 6} g/mol, wherein the weight percentage is based on the total weight of the porous polyethylene;
b) a porosity of at least 40%;
c) Gurley number less than 200 seconds
A porous polyethylene membrane comprising a; And
B) a hydrophilic polymer that fills at least part of the pores of the porous polyethylene
As a film containing,
The film is
i) an MVTR of 2500 g/m 2 /day or more;
ii) a weight of less than 30 grams/m2; In some cases
iii) can take more than 1000 seconds
The film comprising a. The film according to claim 1, wherein the ratio of the matrix tensile strength of the film in two orthogonal directions is in the range of 0.5 to 2.0. The film according to claim 1 or 2, wherein substantially all of the pores of the porous polyethylene membrane are filled with a hydrophilic polymer. The film according to any one of claims 1 to 3, wherein the hydrophilic polymer is a polyurethane, polyamide, polyester, ionomer, or copolymer or a copolymer or combination thereof. The film according to any one of claims 1 to 4, wherein the porous polyethylene membrane comprises a weight of less than 10 grams/m 2. The film according to any one of the preceding claims, wherein the porous polyethylene membrane comprises a porosity of at least 60%. 7. The film according to any one of claims 1 to 6, wherein the porous polyethylene membrane comprises a duration of 60 seconds or less. The film according to any one of claims 1 to 7, wherein the ratio of the matrix tensile strength of the film in two orthogonal directions is in the range of 0.7 to 1.4. The polyethylene membrane according to any one of claims 1 to 8, wherein the polyethylene membrane has a first side and a second side, and a hydrophilic polymer is applied to the first side of the polyethylene membrane to fill at least a portion of the void and the first side of the polyethylene membrane. A film resulting in a cap of the hydrophilic polymer on the phase. The film according to any one of claims 1 to 9, wherein the weight ratio of porous polyethylene to hydrophilic polymer is in the range of 30 to 0.5. An article comprising the film of claim 1. 12. The article of claim 11, wherein the article is a multilayer laminate comprising at least one other layer laminated to a film. The article of claim 11 or 12, wherein the at least one other layer is a textile layer, a polymer film layer, a natural leather layer, a synthetic leather layer, a fleece layer, or a combination thereof. 14. An article according to any of claims 11 to 13, wherein at least one other layer is a textile layer. 15. The article of any of claims 11-14, wherein the layers of the laminate are adhered to each other using a continuous or discontinuous adhesive. 16. The article of any of claims 11-15, wherein the adhesive is a thermoplastic or crosslinkable adhesive. 17. The article of any of claims 11 to 16, wherein the article is a garment. 18. The article of claim 17, wherein the garment is a jacket, coat, shirt, trousers, gloves, hat, shoes, coveralls, or at least a portion thereof. 19. The article of claim 17 or 18, wherein the film is on the outside of the garment or the film is not on the outside of the garment. 20. The article of any of claims 17-19, wherein the garment is waterproof.